Polymerizable and polymerized compositions comprising an o-allylisourea



Patented Oct. 13, 1953 UNITED STATES PATENT OFFICE POLYMERIZABLE AND POSITIONS COMPRIS UREA John A. Price,

a corporation of POLYMERIZED COM- IN G AN O-ALLYLISO- Stamford, Conn., assignor to American Cyanamid Company,

Main

N Drawing. Applica Serial N New York, N. Y.,

tion October 24, 1951, 0. 253,005

16 Claims. (Cl. 26.0--77.5)

This invention relates to the production of new materials having valuable and isourea, e. g, O-allyhsourea itself, the formula for which is: I O-CH2CH=CH2 H2N- =NH an N-monolkyl-O-allylisourea, an N,N-dialkyl- O-allylisourea, an -monoaryl-O-allylisourea, an N,N-diary1-O-allylisourea, etc., and (2) from about 25% to about 99% of a compound which is practicing the present invention are preferably those embraced by the general formula II R NC=NH R o-cmc11=om in which R is a member of the group consisting of hydrogen, alkyl and aryl, the Rs being the Illustrative examples of alkyl a new class of copolymers or interpolymers for use in industry.

Still another and important object of the invention is the production of copolymers or intermonomers, e. g., tion products With acid dyes, than polymers of acrylonitrile or other non-basic monomer alone, or

suggested copolymers of 1) acrylonitrile (or other non-basic monomer) and (2) another different monomer or monomers.

and examples which follow.

The foregoing objects are attained by copolymerization of an O-allylisourea with one or more 20%, of an O-allylisourea, e. g. O-allylisourea, N,N-diethyl-O-allylisourea, etc.,

99% to about or of a comonomer (or comonomers) containing one or more CH2=C groupings. Heat, light or heat and light can be used to efiect or to accelerate polymerization of given hereinafter.

Examples of monomers (comonomers) containing a CH2=C grouping that can be copolymerized with an O-allylisourea, e. g., N-monon-propyl-O-allylisourea, N-monophenyl-O-allylisourea, N,N dixylyl O allylisourea, N,N-di- (phenylethyl) O allylisourea, N monocyclohexyl-O-allylisourea, N monobenzyl-O-allylisourea, N-monotolyl-O-allylisourea, in the weight proportions hereinbefore mentioned, singly or a plurality (two, three, four or any desired number) thereof, the latter often being desirable in order to improve the compatibility and copolymerization characteristics of the mixture of monomers and to obtain new and valuable copolymers having the particular properties desired for a particular service application, are such monomers as the unsaturated alcohol esters, more particularly the allyl, methallyl, crotyl, 1 chloroallyl, 2 chloroallyl, cinnamyl, vinyl, methvinvl, l-nhenvl llyl. hutenyl. etc., esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic. acids such, for instance, as acetic, propionic, butyric, valeric, caproic, acrylic and alpha-substituted acrylic (including alkacrylic, e. g., methacrylic, ethacrylic, propacrylic, etc., and arylacrylic, e. g., phenylacrylic, etc.), crotonic, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, furnaric, citraconic, mesaconic, itaconlc, acetylene dicarboxylic, aconitic, benzoic, phenylacetic, phthalic, terephthalic, benzoylphthalic, etc., acids; the saturated monohydric alcohol esters, e. g., the methyl, ethyl, propyl, isopropyl, butvl. sec.-butyl, amyl, etc., esters of unsaturated aliphatic monobasic and polybasic acids, illustrative examples of which appear above; vinyl cyclic compounds (including monovinyl aromatic hydrocarbons), e. g., styrene, mand pchlorostyrenes, -bromostyrenes, -fiuorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, the various polysubstituted styrenes such, for example, as the various di-, triand tetra chlorostyrenes, -bromostyrenes, -fluorostyrenes, -methylstyrenes, ethylstyrenes, cyanostyrenes,

etc., vinyl naphthalene, vinylcyclohexane, vinyl furane, vinyl nyridine, vinyldibenzcfuran, divinyl benzene, trivinyl benzene, allyl benzene, diallyl benzene, N-vinyl carbazole and the various allyl cyanostyrenes; the various alpha-substituted styrenes and alpha-substituted ring-substituted styrenes, e. g., alpha-methyl styrene, alphamethyl-para-methyl styrene, etc.; unsaturated ethers, e. g., ethyl vinyl ether, diallyl ether, ethyl methallyl ether, etc.; unsaturated amides, for instance N-allyl caprolactam, acrylamide, and N- substituted acrylamides, e. g., N-methylol acrylamide, N-allyl acrylamide, N-methyl acrylamide, N-phenyl acrylamide, etc; unsaturated ketones, e. g., methyl vinyl ketone, methyl allyl ketone, etc.; methylene ma-lonic esters, e. g., methylene methyl malonate, etc; butadienes, e. g., 1,3- butadiene, 2-chlorobutadiene, etc; unsaturated polyhydric alcohol (e. g., butenediol, etc.) esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids, illustrative examples of which appear above; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, glycidyl allyl phthalate, etc.

Other examples of monomers that can be ccpolymerized with an O-allylisourea, e. g., N- methyl-O-allylisourea, to produce my new copolymer compositions are the vinyl halides, more particularly vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, and the various vinylidene compounds, including the vinylidene halides, e. g., vinylidene chloride, vinylidene bromide, vinylidene fluoride and vinylidene iodide, other comonomers being added if needed in order to improve the compatability and copolymerization characteristics of the mixed monomers.

Other and more specific examples of monomeric materials which can be mixed 1; blend d with an O-allylisourea, e. g., N-ethyl-O-allylisourea, in the aforementioned proportions, and the resulting homogeneous or substantially homogeneous, polymerizable composition then polymerized, as hereinafter more fully described, to yield new and valuable copolymer compositions are the allyl compounds which are different from the basic monomer used in practicing the present invention and especially those which have a boiling point of at least about 60 C. Of the monomeric materials which can be used the allyl esters form a large class. The reactive allyl compounds employed are preferably those which have a high boiling point such, for example, as diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl succinate, etc. Other allyl compounds which are not necessarily high boiling also may be used.

Additional examples of allyl compounds, and of other compounds containing one or more CH2=C groupings that can be used in producing the new and useful copolymers or interpolymers of the present invention, are given in, for example, Drechsel and Padbury Patent No. 2,550,652 dated April 24, 1951, and especially in that portion thereof with particular reference to monomers used in forming copolymers with diallyl cyanamide.

Among the comonomers which are preferred for use in carrying my invention into effect are the vinyl compounds which are difierent from the primary basic monomer employed, including the vinyl aromatic compounds, more particularly the vinyl aromatic hydrocarbons (e. g., styrene, the various dialkyl styrenes, etc), and the vinyl aliphatic compounds, e. g., acrylonitrile, acrylamide, etc., and other and different compounds containing a CI-Iz:C grouping, e. g., isopropenyl toluene, the various substituted acrylonitriles (e. g., methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, etc.), the various substituted acrylamides (e. g., methacrylamide, ethacrylamide, the various N-substituted acrylamides and alkacrylamides, for instance N-inethylol acrylamide, N-monoallwl and -diallyl acrylamides and methacrylamides, e. g., N-monomethyl, -ethyl, -propyl, -butyl, etc., and N-dimethyl, -ethyl, -propyl, -butyl, etc., acrylamides and methacrylamides, N-monoaryl and diaryl acrylamides and alkacrylamides, e. g., N-monophenyl and -diphenyl acrylamides and methacrylamides, etc.),' vinyl esters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl acrylate, vinyl methacrylate, etc., esters of an acrylic acid (including acrylic acid itself and the various alpha-substituted acrylic acids, e. g., methacrylic acid, ethacrylic acid, phenylacrylic acid, etc.), more particularly the alkyl esters of an acrylic acid, e. g., the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tertbutyl, amyl, hexyl, octyl, decyl, dodecyl, etc., esters of acrylic, methacrylic ethacrylic, phenylacrylic, etc., acids, including the alkyl acrylates containing not more than four carbon atoms in the alkyl grouping, examples of which are given above, as well as other vinyl aromatic and vinyl aliphatic compounds, and other compounds containing a CHz=C grouping.

Any suitable means may be used in effecting polymerization of the admixture of the O-allylisourea, e. g., N-butyl-O-allylisourea, and one or more other monomers which are copolymerizable therewith. As has been mentioned hereinbefore heat or light or both, with or without a polymerization catalyst, can be used. Ultraviolet light is more effective than ordinary light. Preferably a polymerization catalyst is employed. Any of the polymerization catalysts which are oxide, dioleyl peroxide, distearyl peroxide, di- (tert.-butyl) peroxide and di-(tert-amyl) perperoxides, e. g, tert.-buty1 hydrogen peroxide (tert.-butyl hydroperoxide), tert.-amyl hydro gen peroxide (tert.-amy1) .hydroperoxide), etc.;

names as acetyl peroxide, propionyl peroxide, lauryl peroxide, sucoinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc; fatty oil acid persulfate, sodium persulfate, potassium persulfate, sodium percarbonate, potassium percarbonate, sodium of other catalysts that can be employed are given in the aforementioned Drechsel and Padbury Patent No. 2,550,652.

The concentration of the catalyst employed or 4 or more parts of catalyst per 100 parts of a copolymer. In the latter case, various inert organic solvents may be employed, depending generally is used. I

The polymerization also can be efiected by conventional bulk polymerization technique, in

be effected by a continuous process as well as by a batch operation.

The temperature of polymerization of the polymerizable "composition, atfatmo'spheric er slightly above atmospheric pressure and in the used, the rapidity of polymerization wanted-and With certain cate. g., temperatures ranging between C. and 0 C. or 10 C. At the lower temperatures below Any suitable inhibitor can be used, e. g, tannin, phenol, hydroquinone, ascorbic acid, isoascorbic acid, phenyl-a-naphthylamine, N,N'-di-2-naphthyl-p-phenylenediamine, certain cupric salts, e. g., cupric acetate, etc.

played in an amount .not exceeding 3%, gen

erally less than 1%, by Weight of the monomer or mixture of comonomers, e. g., from 0.01% to 0.5% or 0.6% by weight thereof.

In order that those skilled in the art may betcarried into effect, the following examples are given by way of illustration and not by way of limitation. All parts and percentages are by Example 1 condenser, thermometer and gas-inlet tube, is placed in a constant-temperature bath which is maintained at 35 C. To the vessel is added a solution-of 53-;0parts of acrylonitrile, 900 parts of distilled water and 0.29 part of sulfuric acid; A rapid surface of the solution gen now is then reduced to about one bubble per second. A reduction-oxidation catalyst system (redox system) consisting of 1.71 parts of ammonium persulfate and 0.71 part of sodium metabisulfite, each dissolved in 50 parts of water, is then added. The solution first becomes cloudy at the end of 3 minutes, and the polymerization is fairly exothermic for the first half hour. The polymerization is continued for a total of 4 hours at 35 C. The polymer is collected on a Biichner funnel, and washed with 1000 parts of distilled water followed by about 160 parts of methanol. The polymer is dried in an oven at 70 C. for about 16 hours. The yield of dry polyacrylonitrile, which is white, amounts to 48 parts.

Example 2 A reaction vessel, equipped with a stirrer, reflux condenser, thermometer and gas-inlet tube is placed in a constant-temperature bath which is maintained at 35 C. To the vessel is added a solution of 50.35 parts of acrylonitrile, 2.65 parts of N,N-dimethyl-O-allylisourea, 900 parts of distilled water and 1.0 part of sulfuric acid. The pH of this solution is 3.3. A rapid stream of prepurified nitrogen is passed over the surface of the solution for 30 minutes. The nitrogen flow is then decreased to about one bubble per second. To the vessel is now added 1.71 parts of ammonium persulfate and 0.71 part of sodium bisulfite (meta), each dissolved in 50 parts of water. The polymerization is carried out for hours at 35 C. The copolymer is collected on a Biichner funnel, washed with 1,000 parts of deionized water and dried in an oven at 70 C. for about 16 hours. The yield of dry, white copolymer of acrylonitrile and N,N-dimethyl-O-allylisourea amounts to 48.5 parts, a portion of which is used in the dye tests described in a later example.

Example 3 Exactly the same procedure is followed as described under Example 2 with the exception that instead of 2.65 parts of N,N-dimethyl-O-allyl isourea there is used 2.65 parts of N,N-dicyclohexyl-O-allylisourea and 0.48 part of sulfuric acid instead of 1.0 part. A good yield of a solid copolymer of acrylonitrile and N,Ndicyclohexyl O-allylisourea is obtained. A portion of the dry copolymer is used in the dye tests described in a later example.

Example 4 Same as in Example 2 with the exception that there are used 47.? parts instead of 50.35 parts of acrylonitrile, 5.3 parts of N,N-dibenzyl-O- allylisourea instead of 2.65 parts of N,N-dimethyl- O-allylisourea and 0.91 part instead of 1.0 part of sulfuric acid; also, the time of polymerization is 8 hours instead of 5 hours at 35 C. A portion of the resulting solid copolymer of acrylonitrile and N,N-dibenz.yl-O-allylisourea is employed in the dye tests described in a later example.

Example 5 In this example, too, exactly the same procedure is followed as described under Example 2 with the exception that the N,Ndimethyl-O allylisourea is replaced with an equal weight of N,N-diethylO-allylisourea, 0.88 part of sulfuric acid is used instead of 1.0 part and the polymerization time at 35 C. is 6 hours. The yield 8,. of dry copolymer of acrylonitrile and N,N-diethyl- O-allylisourea amounts to 43.5 parts. A portion of the dry copolymer, which is cream-colored, is employed in the dye tests described in a later example.

Example 6 Same as in Example 2 with the exception that there are used 51.94 parts instead of 50.35 parts of acrylonitrile, 1.06 parts instead of 2.65 parts of N,Ndimethyl-O-allylisourea, and 0.4 part instead of 1.0 part of sulfuric acid. A portion of the resulting solid copolymer of acrylonitrile and N,Ndimethyl-O-allylisourea is employed in the dye tests described in a later example.

Example 7 Exactly the same procedure is followed as described under Example 2 with the exception that instead of 2.65 parts of N,N-dimethyl-O-allylisourea there is used 2.65 parts of O-allylisourea (Formula I), and 1.3 parts instead of 1.0 part of sulfuric acid. A good yield of a solid copolymer of acrylonitrile and O-allylisourea is obtained.

Example 8 Same as in Example 2 with the exception that there are used 45.05 parts instead of 50.35 parts of acrylonitrile; 7.95 parts of N,N-diphenyl-O- allylisourea instead of 2.65 parts of N,N-dimethylhours at 60 C. A portion of copolymer of acrylonitrile and N,N-diphenyl-O- allylisourea is employed in the dye tests described in a later example.

Example 9 2 with the exception that there are used 42.4 parts instead of 50.35 parts of acrylonitrile; 10.6 parts of N,N-ditolyl-O-allylisourea instead of 2.65 parts of N,N-dimethyl- O-allylisourea; 1.83 parts of sulfuric acid instead of 1.0 part; and the polymerization time is 12 hours at 65 C. A portion of the resulting solid copolymer of acrylonitrile and N,N-ditolyl-O- allylisourea is employed in the dye tests described in a later example.

In the same manner 2 to 9, inclusive, compositions comprising other copolymers of copolymerizable ingredients including, by weight, (1) from 1% O-allylisourea, more particularly an N,N-diall yl- O-allylisourea (e. g., N,N-dimethyl-O-allylisourea, N,N-diethyl-O-allylisourea, etc.) an N,N-diaryl-O-allylisourea (e. g., N,N-diphenyl- O-allylisourea, etc.) and other N,N-substitutedor N,N-unsubstituted-O-allylisoureas, and. (2) from to 99% of a vinyl compound, numerous examples of which have been given in the specification prior to the examples, can be produced. A more specific example of a class of copolymers within the aforementioned broad class are copolymers of mixed monomers consisting of from about 2% to about 15% by weight of an N,N-dialkyl-O- allylisourea and the remainder acrylonitrile.

Example 10 A tripolymer of (1) a vinyl aliphatic compound, specifically acrylonitrile, (2) an alkyl ester of an acrylic acid, more particularly such an ester containing not more than 4 carbon atoms in the alkyl grouping, and specifically methyl acrylate, and (3) an N,N-diall yl-O-allylisourea, specifically N,N-dimethyl-O-allylisourea, is produced by following exactly the sameprocedure given under Example 2 with tion that there methyl acrylate in addition to 2.65 parts of N,N- dimethyl-O-allylisourea; time at 35 C. is 6 hours Emample 11 of the homopolymeric acrylonitrile of and of the copolymers of Examples 2 to 10, inclusive, are subjected to the following dye test:

A sample parts) of the dry polymer or copolymer is added to a dye bath consisting of Samples Exa pie 1 O-allylisourea, e. g., O-allylisourea itself and the N,N (hydrocarbon substituted) O allylisoureas, thereby to obtain a copolymeric acryloimproved dyeability is therefore quite apparent.

Example 12 To a reaction vessel are charged parts of acrylonitrile, 10 parts of N,N-climethyl -O-allylisourea and 0.2 part of a,a-azodiisobutyronitrile. The vessel is flushed with nitrogen gas and then temperature of 60 70 C.

To a reaction vessel equipped as in Example 2 are charged 5 parts N ,N -dimethyl-O-allylisourea, 45 parts ethyl acrylate, 200 parts water, 2 parts oxide polymerization catalyst, specifically benzoyl peroxide. The emu tained at 60 Example 14 Exactly the same procedure is Example 13 with the exception The Example 15 vessel equipped as in Example 2 parts N ,N -diethyl-O-ally'lisourea, acetate, parts Water and 0.4

The resulting C. for 8 hours.

To a reaction of other synthetic resins.

Example 16 To a reaction vessel equipped as in Example 2 are charged 2.5 parts O-allylisourea (N,N-unsubstituted-O-allylisourea) Nine parts of methyl-O-allylisourea and Example 18 A spinning solution is 475 parts of N,N-dimethyl-O-allylisourea-acrylonitrile copolymer (obtained by polymerizing a reaction takes sodium thiocyanate (about 50% NaSCN in waaverage molecular ,000 as calculated from viscosity measurements using the Staudinger equation. The resulting solution is filtered, placed under vacuum and allowed to deaerate for about 66 hours. The solution contains about 9.88% of Its viscosity, as measured by the time required for a Monel ball (one-eighth inch in diameter and weighing 0.1418 gram) to fall through 20 cm. of solution at 61 C., is 25.3 seconds.

The solution is spun into a fiber by extruding it through a spinneret, having 40 holes 90 in diameter, into a coagulating bath comprising water maintained at a temperature of about C. The spun fiber in gel state is continuously passed over a pair of converging wash rolls while it is advancing in a helical path. The fiber is rinsed with water on the rolls to remove excess thiocyanate. The washed fiber is stretched 850% by passing it through a bath of hot water maintained at a temperature of about 99.5 C., and then is taken up on bobbins where it is kept in a gelled state by applying a fine spray of water while the fiber is being collected on a bobbin. Additional information on the spinning conditions are given below:

Extrusion rate 3.6 cc. per minute Temperature of the solution at the spinning head Pullaway speed Bobbin speed Calculated denier of the fiber 89 Individual swatches of the gelled fiber are dried at room temperature and then are dyed in the same manner as described under Example 11. The fibers are dyed to a deep shade of blue. In marked contrast, a fiber similarly prepared from homopolymeric acrylonitrile remains colorless when placed in the same dye bath for the same length of time.

Although the new copolymers of this invention are particularly useful in the formation of fibers or filaments which are more amenable to dyeing than homopolymeric acrylonitrile, they also have numerous other applications in the plastics and coating arts. For instance, with or without a filler or other additive, they may be used as molding compositions (or as components of molding compositions) from which molded articles are produced by molding the compositions under heat and g., temperatures of the order of 130 C. or 140 under pressures up to 10,000 pounds or more per square inch. Among the fillers that can be employed in the production of molding compositions are alpha-cellulose pulp, asbestos fibers, cotton fiock, chopped cloth cuttings, glass fibers, wood fiour, antimony oxide, titanium dioxide, sand, clay, mica dust, diatomaceous earth, etc.

The polymerizable compositions of my invention can be used in the production of castings of any desired shape or size; as adhesives; treatment of paper or paper stock; in coating compositions; and for various other purposes. The copolymer can be formed in situ after application of the monomeric mixture to the base material to be coated, impregnated or otherwise treated.

Fibers can be produced from the copolymers of the present invention in the manner described 4.35 meters per minute 45.5 meters per minute in the in, for example, Patents 2,558,730, -731 and 733 with particular reference to the production of a" molecularly oriented fiber from homopolymeric or copolymeric acrylonitrile. The unoriented and oriented fibers produced from my new copolymers are readily dyed, especially with an acid dye, while the fiber is in either a drogel or aquagel) or a dry state.

The new materials (polymerizable compositions and polymerization products) of this invention have numerous other uses, for example uses such as are given in the aforementioned Drechsel and Padbury Patent No. 2,550,652.

The monomeric O-allylisoureas used in producing the new copolymers disclosed and claimed herein also may be polymerized alone to form homopolymers which are useful in industry, e. g., as a modifier of polymeric 0r copolymeric nitrile (wherein no basic monomer is chemically combined in the copolymer) to improve the dyeability of the acrylonitrile polymerization product, especially toward acid dyes. Copolymers also can be produced from a mixture of copolymerizable monomers consisting of substantially more than by weight thereof of an O-allylisourea and the remainder a different compound containing a CH2=C grouping. In general, however, such proportions yield copolymers having no particular advantages, for the usual applications, over the products obtained by polymerizing a mixture of comonomers that contains 75% or less, by weight, of an O-allylisourea; and have the disadvantage, in general, of yielding a monomeric mixture which is less responsive to the usual polymerization conditions, e. g., time, temperature and catalyst required.

I claim:

1. A polymerizable composition comprising, by weight, (1) from about 1% to about 75% of an O-allylisourea represented by the general formula where R is a member of the group consisting of hydrogen, alkyl radicals and aryl radicals and (2) from about 25% to about 99% of a compound which is different from the compound of (1), is

copolymerizable therewith and which contains a CH2=C grouping.

- 2. A product comprising position of claim 1.

3. A composition comprising a copolymer of copolymerizable ingredients including, by weight, (1) from 1% to of an O-allylisourea represented by the general formula R o-o112oH=oH1 where R is a member of the group consisting 0 hydrogen, (2) from to 99% of a vinyl compound.

4. A composition as in claim 3 whereinthe O-allylisourea is an N,N-dialkyl-O-allylisourea.

5. A composition as in claim 4. wherein the the polymerized com- N,N-dialkyl-O-allylisourea is N,N-dimethyl-O allylisourea.

6. A composition as in claim 4 wherein the N,N-dialkyl-O-allylisourea is allylisourea.

7. A composition as in claim 3 wherein the Oallylisourea is an N,N-diaryl-O-allylisourea.

8. A composition as gel (e. g., hy-

acrylo- .alkyl radicals and aryl radicals and in claim 3 wherein the arcrylic acid.

14. A composition as in claim 13 wherein the alkyl ester acrylonitrile.

16. The method of preparing a new synthetic composition which comprises polymerizing, with the aid of a polymerization catalyst, a polymerl4 izable mixture containing, by weight, (1) from 1% to about 75% of an O-allylisourea represented by the general formula where R is a member of the group consisting of hydrogen, alkyl radicals and aryl radicals and (2) from about 25% to about 99% is different from the of (1), is copolymerizable therewith contains a CH2=C grouping.

JOHN A. PRICE.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Caldwell Mar. 13, 1951 OTHER REFERENCES Canadian Journal of Research, vol. 17, sec. B, 1939, page 393.

Number 

1. A POLYMERIZABLE COMPOSITION COMPRISING, BY WEIGHT, (1) FROM ABOUT 1% TO ABOUT 75% OF AN O-ALLYLISOUREA REPRESENTED BY THE GENERAL FORMULA 